Nitrogen-containing organinc compound



i 45 pyridine and themixture is heatedwith stirring bath for several hours. On cooling a white, 45

Patented June "4, 19 40 I a UNITED STATES PATENTIVO'FFIC'E.

mmoonn-coummme oaeamc COMPOUND Henry Alfred Piuott and John Donald Bose,

I Biackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation oi Great Britain No Drawing. Application June 13, 1938, Serial N0. 213,516. In Great Britain June 18, 1937 9 Claims. (01. 260-295) The present invention relates to the manucrystallized from ethyl alcohol. The following iacture of new nitrogen-containing organic comequation illustrates the reaction involved in makpounds, which contain in their molecules at least ing this new compound: one amine (secondary or tertiary) or one subcicmcniunconmncwcmm T I v ii stituted ammonium group. i t i According to the invention a reactive ester of (ham ahydroxyalkyl or hydroxyacyi urea, or of a hydroxyalkyl carbamate or a salt of such an Example 3 ester, is caused to interact with an aliphatic (inl0 eluding cycloaliphatic and'araliphatic) or hetero- 13. parts of cmmcety1urea'-5o parts of cyclic amme The new compounds are mm} m acne and 17 parts of piperidine are heated tothe treatment of texme materials; gether at 100 C. for 2 hours in a vessel fitted By the term reactive ester is meant esters of with reflux condenser From the benzene the halogen acidson aromatic sulphonic km mixture, filtered hot, there separates on cooling a new compound, viz., plperidylacetyl urea, -M. P.

z ggg s g mg at? g g gg gs g ggfi 118 C. The tollowlng'equation illustrates the Thin, as halcgenoalkyl or halogenoacyl we or reaction involved in making this new compound: halogenoalkyl carbamates there come to be con- ClCHaCONHCONHa+C5HmNH- sidered chloroacetyl-urea, iodo-acteyl-urea, 2- CtHioNCHiCONHCONH: chloroethyl-urea or l-chloropropionyl-urea, 3- Example 3 chloropropyl-urea and z-chloroethyl carbamate.

When an aromatic sulphonic ester is used the P t Of o yl 3 Parts f N- starting material can conveniently be used with- Pip dine and 50parts of acetone are heat d out isolation so that the making of th t r gether at'60-70 C. for 14 hours in a vessel fitted 5 and the production thence of a new compound w a reflux condenser- A Whitfi crystalline according to the invention are eiiected as a onemass separates m h ix r This is filtered stage operation. oil.

As aliphatic or heterocyclic amines we may use The Bil-Obtained ureldoacetyl-N-benlyl Pip methylamine, ethylamine, dimethylamine, d1- dinium iodide, crystallised from ethyl alcohol ethylamine, triethylamlne, benzym m cycloforms colorless crystals, M. P. 182 C. The fol- 30 hexylamine, piperidine, N-benzylpiperidine, N- lowing equation illustrates the reaction involved methylpiperidine, pyridine, a-picoline, 'quinoline in making this new comp or tertiary bases themselves prepared by the interaction 0! a halogenoalkylor haiogenoacyl- ICHCONHGONHfimmCmNmHm CHCH,

urea or halogenoalkyl carbamate with a suitable c H '35 secondary amine. a S 1 The invention is illustrated but not limited by o w l I 011:0 NHO ONE: the following examples in which the parts are by Example 4 w i ht. 40 e g Example 1 Y 10 parts of p-toluene sulphonyi chloride is 40 added a little at a time to astirred mixture of 5.2

43 Parts of z'cmmwthylm'ea hydrochmlide parts of fl-hydroxyethylurea and 20 parts of dry (m treating rdr t y u ea w pyridine, the temperature being kept below 30 thionyl hlori are m d w part-inf c. The mixture is then heated on the steam at C. for Z'hours. On cooling the mass be.- crystalline, hygroscopic solid separates. This comes pasty by separation oi crystals. These are substance is a ureidoethylpyridinium salt. The

filtered oil, washed with acetone and dried. The corresponding picrate, M. P. Nil-9C., is idennew compound, ureidoethylpyridinium chloride, tieal with the pici'ate derived from the ureido- 50 forms colourless crystals, M. P. 164 C. when ethylpyridinium chloridevoi Example 1. 5o

Example 5 parts of chloroacetylurea and 40 parts of pyridine are heated together for 5 hours at 100 0. ma vessel fittedwith a reflux condenser. The mixture is then cooled, whereupon crystals separate from the solution. These are filtered off and dried. There is thus obtained ureidoacetylpyridinium chloride, M. P. 230 C. (with decomposition). The following equation illustrates the reaction involved in making this new compound: 1

Example 15 parts of diethylamine, 13.6 parts of chloroacetylurea and 50 parts of benzene are heated together for 1 hour at 100 C. in a vessel fitted with a reflux condenser. The mixture is filtered hot and then allowed to cool, whereupon crystals separate out. There is thus obtained diethylaminoacetylurea, M. P. 100 C. The following equation illustrates the reaction involved in making this new compound:

CICH2CONHCONH2+ (Cal-Is) 2NH- can) aNCI-IzCONHCONHz.

Example 7 To a solution of 'y-chloropropyiurea (prepared as described below) parts of pyridineare added and the mixture is heated at 100 C. for 1 hour. The mixture is then allowed to stand at room temperature 'for several hours, during which time a resinous substance separates out from the solution. The pyridine is removed by decantation and the resinous substance is well washed with acetone, whereupon it solidifies to a-white solid.

.There isthus obtained "y-ureidopropylpyridinium chloride, which, after recrystallisation from ethanol, has M, P. 170 C.. The following equation illustrates the reaction involved in making this new compound:

ClCHrCHaCHiNHCONHfiCtHaN The solution of y-chloropropylurea referred to is conveniently prepared as follows:

15 parts of. 'y-aminopropanol and 200 parts of water are heated to 60 C; and 25 parts of nitrourea are gradually added. Ellervescence occurs, and a gas is evolved. When the eil'ervescence has ceased the clear solution so obtained is boiled under a reflux condenser for 2 hours. The water is then removed by evaporation underdiminished pressure. To the 'y-hydroxypropylurea so. obtained, 28 parts of thionyl chloride are gradually added, the mixture being contained in a vessel provided .with an external cooling jacket and with a refluxcondenser. A violent reaction occurs. When thishas ceased the mixture is heated to C. for 30 minutes. I There is thus obtained a solution containing t chloropropylurea'. which is further treated as described above.

Example 8 10. parts of chloroethyl carbamate and 10 parts of pyridine are heated together at 100 C. for 10 hours in a vessel fitted with a reflux condenser.

A whitecrystalline solid separates out-from the mixture. This is filtered oil and dried. There is thus obtained carbamyloxyethyl-pyridinium chloride of the formula cammcn-cm-em-ocm-nm in the form of white crystals. These, when recrystallised from ethanol, have M. P. 122 C.

Example 9 40 parts of p-chloroethylurea hydrochloride (made. from p-hydroxyethylurea and thionyl chloride) and 100 parts of triethylamine are heated together at 100 C. for 5 hours in a vessel fitted with a reflux condenser. The mixture is then cooled, whereupon white crystals separate from the liquid. These are filtered oif. There is thus obtained ,B-ureidoethyltriethylammonium chloride in the form of white hygroscopic crystals.

The following equation illustrates the reaction involved in making this new compound: ClCHzCHzNHCONH:.HCI+(C1H5)IN (C2H5)3N-CH1CHINHCONH1 Example 10 1 We claim:

1. Quaternary ammonium urea derivatives having the general formula:

R R'- -N cH|).YNnc oNm a" Ac in which formula the group as a whole represents the entire molecular structure of a heterocyclic tertiary amine, 'Ac denotes an anion: 2: represents one of the numbers 1, 2, and 3; and Y denotk a bridging group selected from the category consisting of cHHnd-c- 2. Quaternary ammonium urea derivatives having the general formula:

in which formula the CsHsN- as a whole represents the entire. molecular structure of pyridine, Ac denotes an anion, and Y denbtes a. bridging group selected fronnthe category'consisting of v 3. Nitrogen-containing organic compounds selected from the group consisting of tertiary amino urea derivatives having the formula:

R a N(CH2)=Y NHGONHr in which the group as a whole represents-the radical of a secondary amine selected from the class consisting of dialkyl aminesand secondary heterocyclic bases which contain but a single nitrogen atom in the heterocyclic ring, 3: represents one of the numbers 1,

2, and 3; and Y denotes a bridging group selected from the category consisting of and quaternary ammonium urea derivativeshaving the formula:

R- R N(CH:),-Y-NHCONH| a" Ac in which the group R so E 40 the category consisting of 4. Quaternary ammonium urea derivatives 45 having the formula:

R n' (cm-raucous.

R" o lo in which formula the group having the formula:

ture of a tertiary amine selected from the class consisting of trialkyl amines and tertiary heterocyclic bases which contain but a single nitrogen atom in the heterocyclic ring, Ac denotes an anion; 2 represents one of the numbers 1, 2, and 3: and Y denotes a bridging group selected from the category consisting of 5. Quaternary ammonium urea derivatives having the formula:

n R' N(CH ),YNHOONH-z in which formula the group as a whole represents the entire molecular structure of a heterocyclic tertiary amine that contains but a single nitrogen atom in the heterocyclic ring, Ac denotes an anion; a: represents one of the'numbers 1, 2, and 3; and Y denotes a bridging group selected from the category consisting of CH: and g 6, Quaternary ammonium in which formula the group C5HsN;- as a whole representsthe entire molecular structure of pyridine, Ac denotes a halide atom, or represents on of the numbers 1, 2, and 3, and Y denotes a bridging group selected from the category consisting of '7. Ureidoethylpyridinium chloride. -8. Ureidopropylpyridinium chloride. 9. Chlor-pyridinium acetyl urea.

HENRY ALFRED PIGGOII.

JOHN DONALD ROBE.

as a whole represents the entire molecular strucurea derivatives 

